碘化尾汽冷凝回收系统的工艺改进

苯的磺化反应是磺化碱熔法生产工业苯酚的第一道工序。纯苯和浓硫酸反应后，过量的苯蒸汽能否迅速冷凝回收，直接关系到磺化反应速度和反应收率。本文是对磺化尾汽冷凝回收系统。工艺改进的技术总结。技术要点是：将磺化反应条件由正压改为负压，缩短了反应时间，减少了负反应，提高了换热效率，降低了纯苯单耗，增加了产量，解决了制约生产的关键问题，取得了很大的经济效益。     

电镀领域的磺化反应

列举了在电镀领域中实际应用到的各类磺化产物，根据磺化产物在电镀中的作用的不同，对磺酸基团功能特性做了分类概括，以磺化剂的不同，分别列出反应通式和各种磺化产物；对各类磺化反应的优缺点进行了详细阐述和比较。     

氨基磺酸系两性表面活性剂的新合成法及其机理推断

给出了一种以烷基胺、HCHO与无机磺化剂（NaHSO3或Na2SO3）为原料，经由胺羟甲基化、磺化与固相成盐三步反应，合成氨基磺酸系两性表面活性剂的新合成法。同时，基于曼尼奇反应、磺甲基化和N-烷基化等反应的历程，推断了新合成法的反应机理。结果表明，新合成法的收率高（86.7％）；反应主要为亲核加成历程；胺羟甲基化反应pH值高，有利于H^＋的脱离，促进反应正向移动和中间体的稳定；磺化反应体系酸性越强，越有利于中间体上OH的离去，加速反应正向移动；固相成盐反应简单可行；机理推断结果符合实验和相关文献报道的结果。     

2-磺基-4-壬基苯基聚氧乙烯醚的合成工艺研究

以壬基酚为原料，以发烟硫酸作磺化剂，合成了壬基酚磺酸钠；然后以氢氧化钾为催化剂，进行乙氧基化反应得到2-磺基-4-壬基苯基聚氧乙烯醚。分别考察了反应条件对磺化反应和乙氧基化反应的影响；并用IR验证了所合成产物的结构。结果表明：在温度为40℃，磺化剂用量为壬基酚体积的31％，反应时间2h下，磺化产物收率为99.88％；在150℃，0．3MPa，催化剂用量为壬基酚磺酸钠质量的0．5％下2-磺基-4-壬基苯基聚氧乙烯醚的磺化度为87．78％，聚乙二醇的含量为3．51％。     

磺化聚苯乙烯微球固体酸催化制备油酸乙酯研究

采用回流-沉淀聚合法制备单分散聚苯乙烯微球(PS)；然后以氯磺酸为磺化剂，通过磺化反应制备了磺化聚苯乙烯微球。测试其粒径、Zeta电位和酸密度，探讨磺化剂的最佳用量和最佳磺化时间，获得了酸密度为2.56mmol·g^-1的磺化聚苯乙烯微球；并用红外光谱、热重分析等对其化学组成和耐热性能进行表征。将其作为固体酸催化剂，在催化油酸和乙醇酯化制备油酸乙酯中表现出较高的催化活性。当醇酸比为6∶1、反应温度为80℃、反应时间为6 h、催化剂用量为油酸质量的2%时，酯化率可达88.90%。且该磺化聚苯乙烯微球循环使用3次后，催化活性仍可保持初始活性的95%，在工业制备生物柴油领域具有较好的应用前景。     

烷基苯磺化的化学和技术

随着化学工业的发展，磺化反应广泛应用于染料、制药、炼油、合成洗涤剂等工业，目前世界上用于合成洗涤的磺化产物每年达几百万吨。在磺化反应中，不同的磺化剂和工艺条件对原料单耗和产品质量的影响极大。烷基苯的磺化是合成洗涤剂生产中的重要工序，是决定产品质量优劣的关键工序；由于烷基苯磺酸钠在洗涤剂领域中获得很大发展，并且对生产提出了更高的技经要求和质量指标，促使磺化工艺和设备不断革新。本文将对磺化反应机理、热力学、动力学作一初步探讨。     

磺化反应和技术

介绍了用三氧化硫、硫酸和发烟硫酸、氯磺酸、二氧化硫和氯气、硫酰氯、二氧化硫和氧气、亚硫酸盐进行磺化反应（包括硫酸盐化反应）的特点和应用，并简要介绍了三氧化硫磺化和烟酸磺化的生产技术。     

三氧化硫磺化技术简介

本文介绍了SO_3磺化技术。文中简要论述了磺化反应的机理和特点、磺化工艺流程和控制要点以及磺化反应设备的结构。     

废杂多酸制备牛磺酸的工艺研究

叙述了用废杂多酸通过乙醇胺酯化法制备牛磺酸工艺的可行性；比较了用亚硫酸铵和亚硫酸钠作为磺化剂对牛磺酸分离精制的影响。研究表明，在优选的条件下，3#废杂多酸经过酯化、磺化反应可以制得质量较好的牛磺酸，两步反应后牛磺酸总收率为52％。利用苯精制产生的废杂多酸制备牛磺酸，走出了一条变废为宝、环保增效的可持续发展的路子，有效地提高了催化剂的利用率。     

磺化反应工艺研究进展

介绍目前磺化反应工艺的发展现状,对比了三氧化硫(SO3)、浓硫酸、发烟硫酸、氯磺酸、氨基磺酸等磺化剂的性能及其对磺化反应的影响,同时介绍了磺化反应的影响因素、磺化产物的分离测定方法和磺化反应工艺及设备。     

Sulfonation studies of copolymers,graft copolymers,and polymeric gels using phase transfer catalysts

A new sulfonation method using phase transfer catalysts was applied to sulfonate a number of polymer matrices in an aqueous two-phase system. The polymer matrices included in this study are (1) styrene (Sty) and acrylonitrile (AN) copolymers with glycidyl methacrylate (GMA), (2) graft copolymers of cellulose with GMA, and (3) polystyrene and polyacrylate gels containing GMA as comonomer. The presence of polar groups such as AN in the polymer matrix makes the sulfonation easier. For cellulose graft copolymers, the extent of sulfonation was not much affected by the phase transfer catalysts, presumably due to the high polarity and high water uptake capacity of the cellulose base. For other polymer gels, the following factors influence the extent of sulfonation: (1) the method of gel synthesis, i.e., gels synthesized by delayed addition of GMA give a higher degree of sulfonation; (2) the nature of the crosslinking agent, i.e., gels with ethylene glycol diacrylate (EGDA) gives a higher degree of sulfonation than gels with divinylbenzene (DVB); (3) the pore size of the gels, i.e., gels with larger pore sizes gave higher degree of sulfonation; (4) increasing polarity of the backbone structure of gels favors increased sulfonation, e.g., MMA–GMA–EGDA gels give 54% sulfonation, whereas Sty–GME–EGDA gives only 38%.     

Melt synthesis of sulfonated EPDM ionomers in batch and continuous processes

Zinc-neutralized sulfonated EPDM ionomers (Zn-SEPDM) were prepared by batch and continuous melt sulfonation processes, and the ionomer products were compared with ionomers synthesized by sulfonation of EPDM in homogeneous solution. The efficiency of a batch melt sulfonation using an intensive mixer as a reactor was comparable to that of the solution sulfonation process, but the efficiency of the melt sulfonation in a twin-screw extruder was considerably lower, which was thought to be a consequence of a relatively short reaction residence time due to limitations of the equipment. Melt neutralization was not complete, which produced a dark colored product. However, the incomplete neutralization and the color of the product did not affect the mechanical properties of the melt sulfonated ionomers, which were comparable to those of ionomers made by conventional solution sulfonation. The metal sulfonate concentration alone determined the mechanical properties of the ionomer. Melt sulfonation of Zn-SEPDM ionomers by batch or continuous melt processes appears to be a practical alternative to solution sulfonation, but further optimization of the melt sulfonation processes is needed to ensure uniform sulfonation and complete neutralization.     

Sulfonated polysulfone as promising membranes for polymer electrolyte fuel cells

A new, milder sulfonation process was used to produce ion‐exchange polymers from a commercial polysulfone (PSU). Membranes obtained from the sulfonated polysulfone are potential substitutes for perfluorosulfonic acid membranes used now in polymer electrolyte fuel cells. Sulfonation levels from 20 to 50% were easily achieved by varying the content of the sulfonating agent and the reaction time. Ion‐exchange capacities from 0.5 to 1.2 mmol SO₃H/g polymer were found via elemental analysis and titration. Proton conductivities between 10⁻⁶ and 10⁻² S cm⁻¹ were measured at room temperature. An increase in intrinsic viscosity with increasing sulfonation degree confirms that the sulfonation process helps to preserve the polymer chain from degradation. Thermal analysis of the sulfonated polysulfone (SPSU) samples reveals higher glass transition temperatures and lower decomposition temperatures with respect to the unsulfonated sample (PSU). Amorphous structures for both PSU and SPSU membranes were detected by X‐ray diffraction analysis and differential scanning calorimetry. Preliminary tests in fuel cells have shown encouraging results in terms of cell performance. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1250–1257, 2000     

三氧化硫磺化装置的优化设计

简述了三氧化硫磺化技术的发展历程、三氧化硫磺化装置的现状;分别从不同工艺技术单元、磺化关键设备一磺化反应器和控制系统等方面论述了三氧化硫磺化装置的优化设计,节省能源消耗,降低了生产成本,实际生产过程容易控制,保证磺化产品质量有了进一步的提高。     

石蜡裂解α-烯烃制备AOS表面活性剂

以蜡裂解α-烯烃(AO)为原料制备了α-烯基磺酸盐(AOS)。所涉及的主要技术问题是:原料蜡裂解α-烯烃的精制处理,采用发烟硫酸为磺化剂的磺化工艺的优化。实验数据表明,采用蜡裂解AO为原料是可以生产 AOS的;其产物与市售AOS(采用乙烯齐聚α-烯烃合成)相比,色泽深、未磺化物含量高,然而实验室产品具有与市售AOS相当的表面张力,且发泡性能优于市售AOS。     

Post sulfonation of bisphenol A poly(arylene ethers)

In this study, bisphenol A polyetherimide (PEI) was sulfonated by a novel postsulfonation route using trimethylsilylchlorosulfonate. Different degrees of sulfonation were achieved by varying the mole ratio of the sulfonating agent to the PEI repeat unit and the reaction time. Comparison was made with respect to bisphenol A polysulfone (PSU) to study the influence of electron withdrawing group in the sulfonated poly(arylene ethers) (SPAE) backbone on sulfonation. Structural characterization of SPAE was conducted by ¹H‐NMR and FTIR spectroscopy. The enhanced reaction rate with PSU compared to PEI was attributed to the deactivation of bisphenol A unit due to the stronger electron withdrawing effect of imide group. The sulfonation of PEI was also carried out with chlorosulfonic acid for comparative study. The effects of degree of sulfonation on thermal and mechanical properties of SPAE‐s were studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and a tensile testing machine. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

磺化SEBS的制备工艺研究

探究了影响SEBS磺化反应的各种因素。结果表明:较适宜的磺化试剂和溶剂分别为乙酰基磺酸酯和三氯甲烷;随着磺化反应时间的延长和磺化试剂用量的增加,产物磺化度均有不同程度的增大,达到一定程度后,磺化反应趋于平稳;低温反应的平衡磺化度高于高温反应的平衡磺化度,但平衡时间过长;磺化试剂配比n (乙酸酐)∶n (浓硫酸)=2∶1时,产物磺化度达到最大。当磺化试剂配比大于或小于2∶1时,磺化效率均有不同程度的降低。     

聚醚砜的磺化与热性能

以浓硫酸为溶剂 ,氯磺酸为磺化剂对聚醚砜 (PES)进行了磺化 ,制备了不同磺化度的磺化聚醚砜 (SPES)。探讨了反应的影响因素 ,分析了 SPES的热稳定性。结果表明 SPES的 Tg较 PES升高 ,随着磺化度的增加 ,SPES的降解温度降低。     

我国对甲酚化工新进展

论述了我国对甲酚化工的新进展。采用气体SO_3磺化甲苯、高效精馏及参数泵分步结晶新技术制取对甲酚，比传统硫酸磺化法收率高、能耗低、质量好、污染小。     

Mild sulfonated polyether ketone ether ketone ketone incorporated polysulfone membranes for microbial fuel cell application

To address the impediments of low power generation of Nafion, which is the main hurdle in the commercialization of microbial fuel cells (MFC), the current study focuses on developing a new PEM for MFC from mild sulfonation of PEKEKK with relatively improved physiochemical properties. In this study, mild post sulfonation of a polyether ketone ether ketone ketone (PEKEKK) has been successfully achieved using 98% H2SO4 at 90°C under reflux. 5%–30% (wt%) of sulfonated PEKEKK (SPEKEKK) loaded polysulfone (PSU) composite membranes were fabricated via a solution casting method. Ingeminating evidence of the sulfonation and structure of sulfonated polymer was proved by ¹H NMR peaks integration data and FTIR, respectively. The addition of SPEKEKK to PSU showed significant improvement in conductivity owing to the availability of more protonated sites ( SO3H) and water mediated pathways for the conduction of protons. The composite membrane containing 30 wt% SPEKEKK exhibits the highest conductivity of 0.12 S/cm at 90°C. The water uptakes and swelling ratio of the composite membranes are all higher than that of the pristine PSU membrane and show an increasing trend with increasing SPEKEKK content, thus validating the availability of water domains. Meanwhile, the lowest initial decomposition temperatures assigned to sulfonic acid groups and main chain degradation of the polysulfone/polyether ketone ether ketone ketone (PSU/SPEKEKK) composite membranes occurred at ~300°C and ~500°C respectively, which reflects an excellent thermal stability property. The experimental results indicate that the PSU/SPEKEKK membrane has the potential to greatly enhance the efficiency of MFCs.